Yu Fei-Yang, Lang Zhong-Ling, Wang Xian, Sun Jing, Liu Yu-Chen, Tan Hua-Qiao, Ge Jun-Jie, Li Yang-Guang, Kang Zhen-Hui
Macao Institute of Materials Science and Engineering (MIMSE), MUST-SUDA Joint Research Center for Advanced Functional Materials, Macau University of Science and Technology, Macau 999078, China.
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Northeast Normal University, Changchun 130024, China.
Sci Bull (Beijing). 2025 Jul 24. doi: 10.1016/j.scib.2025.07.033.
Pt-based catalysts are prone to oxidation and CO poisoning during the hydrogen oxidation reaction (HOR), leading to deactivation, which has presented significant challenges for the application of proton exchange membrane fuel cells (PEMFC). Here, we propose a dual-protection strategy with the advantages of Pt-polyoxometalates (POMs) and carbon dots (CDs) to synthesize an advanced POMs-CDs based electrocatalyst, Pt-SiW-CDs, with Pt clusters dispersed on SiW-CDs substrates. It exhibited exceptional HOR performance, achieving a mass activity of 10.36 A mg at an overpotential of 50 mV, which is over 54 times greater than that of Pt/C (0.19 A mg). These catalysts also display impressive stability and CO tolerance. By employing X-ray absorption fine structure (XAFS) spectra, transient photovoltage (TPV), transient potential scanning (TPS), and density functional theory (DFT) calculation, the in-depth investigation suggested the muti-roles of SiW and CDs for synergistic enhancement of Pt electrocatalyst stability and activity in HOR process. CDs act as bridges, effectively and rapidly transferring protons and electrons to SiW from Pt clusters. CDs can effectively coordinate with Pt, regulating its electronic structure while pre-occupying Pt sites, thus hindering CO adsorption on Pt. The reduced SiW efficiently transfers electrons to Pt, inhibiting the oxidation of Pt. Additionally, SiW also serves as the driving force, maintaining the rapid progression of the HOR process. The dual-protection strategy provides new ideas and directions for design of efficient and stable heterogeneous catalyst.
基于铂的催化剂在氢氧化反应（HOR）过程中容易发生氧化和一氧化碳中毒，从而导致失活，这给质子交换膜燃料电池（PEMFC）的应用带来了重大挑战。在此，我们提出一种具有铂-多金属氧酸盐（POMs）和碳点（CDs）优势的双重保护策略，以合成一种先进的基于POMs-CDs的电催化剂Pt-SiW-CDs，其中铂簇分散在SiW-CDs基底上。它表现出优异的氢氧化性能，在50 mV的过电位下实现了10.36 A mg的质量活性，这比Pt/C（0.19 A mg）高出54倍以上。这些催化剂还表现出令人印象深刻的稳定性和抗一氧化碳耐受性。通过采用X射线吸收精细结构（XAFS）光谱、瞬态光电压（TPV）、瞬态电位扫描（TPS）和密度泛函理论（DFT）计算，深入研究表明SiW和CDs在氢氧化反应过程中对协同增强铂电催化剂稳定性和活性具有多种作用。CDs充当桥梁，有效地将质子和电子从铂簇快速转移到SiW。CDs可以与铂有效配位，调节其电子结构，同时占据铂位点，从而阻碍一氧化碳在铂上的吸附。还原后的SiW有效地将电子转移到铂，抑制铂的氧化。此外，SiW还作为驱动力，维持氢氧化反应过程的快速进行。这种双重保护策略为高效稳定的多相催化剂设计提供了新的思路和方向。
